Vat dyestuffs



5 preferable to carryout the preparationof the Patented Apr.-16,'1940 Ernst Honold, Frankfort-on the-Main, Heinrich Neresheimer, Ludwigshafen-on-the-Rhine, Max

Schubert, Frankfort-on-the-Main,

Berthold Stein, Mannheim, and Hans Reich, Ludwigs-f hafen-jon-the-Rhine, Germany, assignors, to General Aniline &' Film Corporation, a corporation of Delaware .No Drawing. Application October 8, 1938,'Serlal yNo. 233,978. In Germany ctober 14, 1937 6 Claims; (d sco-152) e present invention relates to vat dyestuffs "'containing azo groups. I I k We .have'fou'nd that vat dyestuffs of valuable properties are obtained by treating vattable compounds which contain an aminoaryl group on a' six-membered ring :iormed only of carbon and nitrogenatoms with oxidizing agents. I p

The six-membered ring containing nitrogen may be for example a pyridine, pyrimidine or 10 pyrazine ring and it may contain, in. addition to the aminoaryl group, for example halogen atoms, alkyl, .aryl hydro xyr or etherified hydroxy groups or attached rings, asfor example benzene or polymethylene rings. Itmaybe attached to a radicle of the anthraquinone, naphthoquinone, H

anthrone,'indigo or thioindigo series or a still "*"higher' ring group. The aminoaryl group may belong'for example to the benzene, naphthalene;

or diphenyl series; v i go As initial materials there may therefore, be mentioned for example aminoaryl derivatives of acidslf ;'They may be allowed 'tofact in acid,"

neutral or alkaline media. In many cases it is I initial r'iia'terials, for exampleTby reduction of the' corresponding nitrov compounds, in one s am: tion with their further treatment.

, In 'so far. as the amino compounds used as in-. 40 itial materials themselveshavedyestuff properties', the oxidation to the new dyestuffs'may also bef carriedout on the fibre'ffor example by treatment of the dyeing with hypochlorite solution. Nitrous acid or substances {yielding the same 5 under the reaction" conditions are unsuitable for the oxidation. because they have a diazotizing .constitution: I

I The new dyestuffs are distinguished by high I iastness, in particular by an excellent fastness to light; They are usually soluble only with great difliculty in' organic solvents.

The following examples will further illustrate how the said invention may be carried out in practice but the invention is not restricted to t these examples. The parts are by weight.

, Example 1 Sodiumhypochlorite solution is added while heating to a suspensionof finely divided paraaminophenyl 2 (N) .1 pyridinoanthraquinone (obtained by thereduction of the para-nitrophenyl.2(N).l-pyridinoanthraquinone of the with sodium sulphide in an alkaline liquid beautiful brown needles from nitrobenzene which dissolve in sulphuric acid giving a. greenish yellow coloration) until the original red-brown precipitate has acquired a pure yellow color.

Instead of acidified hypochlorite solution, there may also be usedfor example free chlorine, alkaline hypochlorite or hypobromite solutions, aqueous permanganate solutions, or chromic anhy dride in glacial acetic acid. i

The new vat dyestuff dyes cotton brown-yellow shades from a violet-red vat. It is a yellow meal which dissolves instrong sulphuric acid-giving a yellow coloration. l Bystartingfrom the corresponding meta-nitro compound instead of from the para nitro compound, a dyestufi is obtained having quite sim-.' ilar properties. Its dyeing on cotton is pale yellow. .1

Example 2 Para-nitrophenyl 2.3 hydroxypyrimidinoanthraquinone:

(obtainable from 2-aminoanthraquinone-S-carbonamide" and para-nitrobenzo'yl chloride"y'ellow needles from nitrobenzene which dissolve I in sulphuric acid giving a yellow-red coloration)" is vatted at 50 C. with alkaline sodium hydro; N 1

(obtainable from para-nitrobenzoyl chloride and 1 aminoanthraquinone fl-carbonmethylamide by sulphite solution and an aqueous solution of potassium permanganate is added to"the'va'tf The liquid until the latter is no longer used up. is boiled for a short time, the mass is filteredby suction While hot and the deposited'pyrolusite 'removed therefrom in dilute acetic acid suspension by the addition of bisulphite.

The vat dyestuil obtained dyes cotton clear? L p 10 fi y dispersed 4l nitro pyc -pheny1--"-1.9 anthrapyrimidine (obtainable by condensing l -aminoanthraquinone. with l-nitrobenzomethylimide chloride in the presence of i nitrobenzene) are added toasolutionof '14 parts of stannous chloride in 200-partsl of 5 er; cent fast yellow shades from a red-brown vat. If a nitro compound of the formula (obtainable from 2-aminoanthraquinone-3 car- Example 3 A vat at 50 C. of 3 parts of para-nitrophenyl- 1 (N) .2-hydroxypyrimidinoanthraquinone:

I|\TO2 (obtainable by the action of. para-nitrobenzoyl chloride on 1-aminoanthraquinone fz-carbona mide in nitrobenzene-brown needles from nitrobenzene dissolving in strongv sulphuric acid to give a green-yellow coloration), 20 parts of. 35,

per cent caustic soda solution, 10 parts of hydrohypochlorite solution containinglZ. percent of active chlorine and 400. parts-ofwater.

L the residueis filteredoff by suctionlwhile hot.

The dyestuff dyes-cotton. brown-yellow shades;

parts of 2'-n itrophenyl-1 (N).2-pyridinoanthra-L.

from a red-brown Vat.

The whole is heated to boiling for a short time and:

If there be used. instead of the above'me'n tioned compound, the N-methyl compound:

I NO: v

boiling inii'itrobenzene-wellow needles'from nitrobenzene dissolving in strong sulphuric acid to give a yellow coloration); a dyestuff is obtained which yields palegyellow dyeings on cotton.

Example 4 sodium hydroxide solution. The mixture then heated at from to C. until the'nitro compound has completely reacted. The resulting product is sucked-off, washed; dried and purified by redissolution from concentrated sulfuric-acid.i a The sulfate obtained thereby is'treatedwith dilute aqueous ammonia. ,I'he azocompound thus: obtained is a yellowpowd'er' which is difilcultlysoluble in organic solvents. It dissolves in con-' centrated sulfuric acid giving a golden-yellow-coloration and dyes cotton from a brownish-red vat-wreddish yellowshades;

Elma

10' parts of finely'dispersed 5-benzoy1'amino-4' I nitro-PyC-phenyl- IB -anthrapyrimidine (obtain The mixture is heated at from 85"" to95 0; until i the nitro compound has disappeared; Tl-1e"-dye+ j stufi is then filtered ofi by suctionQWas'hed. and

dried. By heating its solutions-in concentrated} sulfuric acid'atfrom to c.,'1;hetw"penzoyl groups are split off. The diamino compound" I is then precipitated from the" sulfuric" acid,

8 solution by adding water.

sulfuric acid isre noved by washing out with dilute aqueous ammonia. The dry compound is The remainder of" then treated with benzoyl chloride. whereby the two amino groups are reconverted' into ben-j F zoylamino groups. The new azo compoun'd' forms beautiful yellow needles which arediflicultlysolu ble even in high boiling organic": solvents. "The" dyestuff is, however, soluble in concentrat'edisul dyes cotton from "a brownish red vati: y nowshades. p I

" Exempted pa t f sodi y oidde munch. of v#1505.

Baum-strengthare; added to asuspensionaof 23.

quinone (obtainable by condensing i-aminoanthraquinone-Z-aldehyde with phenylacetaldehyde and treating the resulting 2'-phenyl-1(N).2-pyridinoanthraquinone with nitric acid in the presence of sulfuric acid monohydrate) in 1150 parts of water and the mixture is heated at from 40 to 45 C. By adding 30 parts of pyridine and parts of sodium hydrosulfite a brownish-red vat of the amino compound formed is obtained. After a short time,from 1000 to 1200 parts of a sodium hypochlorite solution having 10 per cent of active chlorine is allowed to flow in and the.

temperature is raised to C. After further heating for a short time at 90 C. the resulting dyestufi is sucked off, washed and dried. It may be purified by way of its sulfate. It dissolves in concentrated sulfuric acid giving a reddish-' orange coloration and dyes cotton from a brownish-red vat yellow shades.

What we claim is: 1. A vat dyestufi corresponding to the general formula XarN=N-ar--X wherein X represents a para-quinoid polynuclear radicle built up by the adding-on of a six-mem-' bered ring having only carbon and nitrogen as ring members, to an anthraquinonic nucleus in positions selected from the 1.2-, the 2.3- and the Lil-positions of the said anthraquinone nucleus;

and ar an arylene ring having upto two noncondensed benzene. nuclei, the radicle ar being combined with the said six-membered nitrogenous ring present in X the groups Xar being the same on both sides of the azo bridge.

2. A vat dyestuif of the general formula wherein A represents an anthraquinonic nucleus and R a pyridine ring, two carbon ring members of A and R being common to both, and ar an arylene ring having up to two non-condensed benzene nuclei, the groups ARar being the same on both sides of the azo bridge.

3. A vat dyestuff of the general formula ARar--N=N--ar--R- -A wherein, A represents an anthraquinonic nucleus and R a pyrimidine ring, three carbon ring members of A and R being common to both, and ar an arylene ring having up to two non-condensed benzene nuclei, the groups A--Rrar being the same on both sides of the azo bridge.

4. The vat dyestufi oi the formula ERNST HONOLD. HEINRICH NERESHEIMER. MAX SCHUBERT. BERTHOLD STEIN.

HANS REICH. 

